ENVIRONMENTAL MONITORING M-1402|2019
Environmental pollutants in the
terrestrial and urban environment
2018
COLOPHON
Executive institution
NILU – Norwegian Institute for Air Research 978-82-425-2986-2 (electronic)
Project manager for the contractor Contact person in the Norwegian Environment Agency
Eldbjørg Heimstad (NILU) Gunn Lise Haugestøl
M-no Year Pages Contract number
1402|2019 186 16078185
Publisher The project is funded by
NILU – Norwegian Institute for Air Research NILU OR 19/2019
NILU Project no. O-117065
Norwegian Environment Agency
Author(s)
Eldbjørg S. Heimstad (NILU), Torgeir Nygård (NINA), Dorte Herzke (NILU) and Pernilla Bohlin-Nizzetto (NILU)
Title – Norwegian and English
Miljøgifter i terrestrisk og bynært miljø 2018
Environmental pollutants in the terrestrial and urban environment 2018
Summary – sammendrag
Samples from the urban terrestrial environment in the Oslo area were analysed for various inorganic and organic environmental pollutants. The selected species were earthworm, fieldfare, sparrowhawk, brown rat, red fox and badger. Air and soil samples were also included in the study to further the understanding on sources and uptake of pollutants. A foodchain approach was used to investigate trophic magnification of the different compounds.
Prøver fra det urbane terrestriske miljøet i Oslo-området ble analysert for flere uorganiske og organiske miljøgifter. De utvalgte artene var meitemark, gråtrost, spurvehauk, brunrotte, rødrev og grevling. Luft og jordprøver ble også analysert for å øke forståelsen av kilder og opptak av miljøgifter. En næringskjedetilnærming ble valgt for å undersøke trofisk magnifisering av de forskjellige stoffene.
4 emneord 4 subject words
POPs, PFAS, tungmetaller, nye miljøgifter POPs, PFAS, heavy metals, emerging pollutants Front page photo
Knut Riise
The Norwegian Environment Agency Summary
On behalf of the Norwegian Environment Agency, the Norwegian Institute for Air Research (NILU) in collaboration with Norwegian Institute for Nature Research (NINA) and Norwegian Institute for Water Research (NIVA) analysed air, soil and biological samples from the
terrestrial and urban environment for various inorganic and organic environmental pollutants.
The monitoring programme has the following key goals:
- Report concentrations of selected environmental pollutants in several trophic levels of a terrestrial food web;
- Compare the concentration of the selected pollutants across samples and species;
- Evaluate potential trophic magnification of the different pollutants using a foodchain approach
This report presents the findings from the sixth year of the urban terrestrial programme.
Samples for this monitoring period was sampled in 2018.
A broad cocktail of environmental pollutants, consisting both of persistent organic pollutants, organic phenolic pollutants, biocides, pesticides, UV compounds, emerging and legacy PFAS, siloxanes, chlorinated paraffins, organic phosphorous flame retardants and metals were measured in air, soil and biota samples. The concentrations of the selected pollutants were compared across species and to data from previous years. In addition, the levels of the various pollutant groups were evaluated for each species. Potential biomagnification was also investigated.
Below follows a short summary for each compound class investigated. Where a comparison of concentrations was performed for hydrophobic pollutants (PCBs, PBDEs, CPs, Cyclic siloxanes, Biocides, UV compounds) between species and organs, this was done on a lipid weight basis.
Metals: As also shown in previous years, toxic metal (Hg, Pb, Cd, As) concentrations were highest in soil. Of the biological matrices analysed, earthworms, brown rats, badger and foxes contained the highest amounts of metals. The pooled sample of two fieldfare eggs from the site Kjelsås showed a Pb concentration of 136 ng/g ww (fieldfare egg from same site had 206 ng/g ww in 2017 and 494 ng/g ww in 2016). This concentration is more than 10-20 times higher than the levels detected in fieldfare eggs from the other sites. A general threshold for adverse physiological effects of Pb is set at 400 ng/g ww in bird blood, however direct comparison between concentrations in bird eggs and bird blood are not recommended. Hg concentrations were highest in earthworm and red fox with median values of 143 and 110 ng/g ww. One rat liver sample had a Hg concentration of 1093 ng/g ww. Cd was highest in badger liver samples, where concentrations in three samples exceeded 2000 ng/g ww.
PCBs: Data across all species revealed that sparrowhawk had the highest median
concentrations of sumPCB of 6974 ng/g lipid weight (lw) followed by fieldfare and red fox with 784 ng/g lw and 550 ng/g lw respectively. One sparrowhawk sample had a high sumPCB value of 1874 ng/g ww. Although this concentration is lower than a general reported NOEL value for wild birds of 4000 ng/g for PCB, potential effects cannot be excluded due to different sensitivity among bird species. PCB-153 dominated in almost all matrices, with the
exception of foxes where PCB-180 dominated, and air where PCB-52 and -101 dominated. The air concentrations of PCBs at the urban sites, especially the sites in Slottsparken (0.91
ng/day) and at Alnabru (0.12 ng/day), were much higher than those measured at background air monitoring stations in Norway, suggesting the urban area to be a source to PCBs.
PBDEs: As shown also in previous years, the levels of PBDEs were lower in all environmental matrices compared to PCB and PFAS. Sparrowhawk eggs had the highest median concentration of sumPBDEs (465 ng/g lw) followed by brown rat liver (224 ng/g lw) and fieldfare eggs (181 ng/g lw). For the egg samples, PBDE-99 had in general higher concentrations than 100, 153 and 47, while BDE-207 and 209 dominated in brown rat liver. As in 2017, one sparrowhawk egg had much higher sumPBDE than the other eggs of 147 ng/g ww. The same egg had also highest sumPCB value. This measured sumPBDE concentration is seven times lower than a threshold level of 1000 ng/g ww for reduction of reproductive performance in osprey. The passive air sampler could detect several PBDE congeners in urban air. The highest
concentrations of sumPBDEs in air were observed at Alnabru (0.48 ng/day) and Slottsparken (0.23 ng/day), and as with PCBs, these levels indicate that the urban area is a source of PBDEs detected in air.
New BFRs: The various compounds in this pollutant class was first and foremost detected in air, soil, earthworm and brown rat. The concentrations of new BFRs were lower than the concentrations of PBDEs in air and sparrowhawk eggs, but higher in the other matrices, primarily due to relatively high concentrations of DBDPE, and partially BTBPE and PBBZ. In air, Alnabru and Slottsparken had highest sum concentrations (0.18 and 0.13 ng/day). The highest median sum concentration of new BFRs was found in fieldfare which had a median concentration of 490 ng/g lw. DBDPE had highest concentrations among the newBFR compounds, but was detected in fewer samples than BTBPE and PBBZ. One extreme concentration of DBDPE was detected in brown rat liver of 940 ng/g ww. We have not been able to relate these levels to any known toxic effect of DBDPE. NOAEL for DBDPE in rat has been determined to be 1000 mg/kg bw/day.
PFAS: The dominating PFAS compound was PFOS in all environmental matrices, except for air where only PFBS and PFHxS were detected. The levels of PFOS in earthworm from Alnabru (69 ng/g ww) in 2018 was much lower than in 2017 (531 ng/g ww). This year, the median
concentration of sumPFAS was high in sparrowhawk (143 ng/g ww) and fieldfare (99 ng/g ww) eggs. The highest PFOS (sum of linear and branched PFOS) concentration was detected in a sparrowhawk egg sample which contained 417 ng/g ww PFOS. This PFOS concentration is lower than a recommended threshold value for hatching success of PFOS of 1900 ng/g ww in bird egg. In agreement with what was found in 2016 and 2017 for fieldfare eggs, the 2018 sample from Grønmo had the highest PFOS concentration of 250 ng/g ww, ten times higher than the mean concentrations of the other fieldfare samples. Fieldfare egg from
Holmenkollen had even higher sumPFAS concentration than the egg from Grønmo due to high concentration of the long-chain perfluorinated carboxylates, where the PFTeA concentration was 137 ng/g ww. Of the new PFAS (6:2 FTS, 8:2 FTS, 10:2 FTS, Cl-PFOS, Cl-PFOA and PFECHS) included in the monitoring in 2018, the compound PFECHS was found in all nine sparrowhawk eggs and in one liver sample from rat. The highest concentration was 2.4 ng/g ww in sparrowhawk egg. The compounds 8:2 FTS and 10:2 FTS were detected in all fieldfare and sparrowhawk eggs. 10:2 FTS was also detected in badger and rat liver. 6:2 FTS and 8:2 FTS were also detected in some samples of rat liver. The highest concentration was 11.8 ng/g ww for 10:2 FTS in fieldfare egg. Cl-PFOS was only detected in one rat liver sample, 1.2 ng/g ww.
SCCPs/MCCPs: Chlorinated paraffins (CPs) were found in most matrices. The lowest detection rate of SCCPs and MCCPs was found in fieldfare. The detection frequency of SCCPs and MCCPs in fieldfare was 50% and 80%, respectively. One sparrowhawk sample and one fieldfare sample had extremely high values of SCCPs and MCCPs. The highest concentration of sumCPs in sparrowhawk eggs was 9722 ng/g ww where MCCPs dominated the sum concentration with 6697 ng/g ww. The fieldfare sample with highest CP concentration was from Bøler and had a sumCP concentration of 6580 ng/g ww where SCCPs dominated the sum concentration with 4730 ng/g ww. A fieldfare sample from the same location had the highest sumCPs in 2017. It is not known if these extremely high concentrations may pose a risk to fieldfare and sparrowhawk. Estimated air concentrations at Slottsparken and VEAS sites were approximately ten times higher than annual mean concentrations measured at background stations in Norway.
Cyclic siloxanes (cVMS): Air samples had high levels of D4, D5 and D6. The highest sumSiloxane concentration of 51 ng/day was found in Slottsparken. The estimated air concentrations in Slottsparken based on uptake rates of D5 and D6 were 100-1000 times higher than the measured concentrations at background stations in Norway. This reflects that there are many emission sources for siloxanes in urban areas. The other matrices revealed very few detectable concentrations. Based on PNEC for predators, the levels of D4, D5 and D6 in earthworms and fieldfare eggs as prey are not high enough to pose any risk for predators.
OPFRs: As with siloxanes, air samples had high loads of OPFR with sumOPFR ranging from 1.04 to 6.82 ng/day. As in 2017, TCPP was the dominating compound, and as with siloxanes, the highest concentration of TCPP and sumOPFR were observed in Slottsparken and at Alnabru. For biological samples, OPFRs were mainly detected in the single pooled sample of soil (sumOPFR of 10.6 ng/g dw) and the pooled earthworm sample (14.4 ng/g ww), as well as the three pooled samples of brown rat (1.8-112 ng/g ww). EHDP (95.6 ng/g ww) had highest contribution to the maximum sumOPFR concentration of 112 ng/g ww in rats.
Dechloranes; were analysed in earthworm, fieldfare, sparrowhawk and red fox. Dechloranes were sparsely detected in earthworms, but Dec-602, Dec-603 and anti-DP were detected in many of the other samples, but at relatively low levels compared to the other pollutants measured in this study. Dec-603 dominated in fieldfare (<LOD-2.23 ng/g ww) and
sparrowhawk eggs (0.37-4.62 ng/g ww) with 90 % and 100 % detection rate, respectively. In fox liver, anti-DP had highest concentrations, but was only detected in 50% of the samples.
The highest median sum concentration of dechloranes was detected in sparrowhawk eggs followed by fieldfare eggs and was 72 ng/g lw (2.9 ng/g ww) and 33 ng/g lw (1.6 ng/g ww), respectively. We have not been able to relate these levels to any effect of dechloranes.
Pesticides; were only analysed in sparrowhawk eggs and the median concentration of SumDDT measured in 2018 was 1222 ng/g ww (mean 1358 ng/g ww). P,p’-DDE was clearly dominating the sumDDT with a median concentration of 1210 ng/g ww. This concentration is higher than a reported PNEC of 870 ng/g ww associated with 20% eggshell thinning in osprey.
Seven of nine eggs from Oslo area exceeded 1000 ng/g ww in 2018, indicating a potential risk for reproductive effects of DDT in birds in this urban environment today.
UV compounds; were detected in some of the pooled samples. UV-327, UV-328 and OC were detected in the three sparrowhawk samples. UV-328 was the dominating compound in liver samples (red fox, badger and brown rat), while OC had highest concentration in one pooled sample of soil, and was the only compound detected in the one sample of earthworm. The highest sum concentration was found in the one pooled earthworm sample and in brown rat liver. Effect levels for these compounds were not found for terrestrial ecosystems.
Biocides (rodenticides); were measured in fox, badger and rat livers. The compounds were mainly detected in red fox liver where bromadiolone and brodifacoum dominated. Only bromadiolone was detected in rat liver at lower concentrations than in fox liver.
Bromadiolone and brodifacoum were generally detected at lower concentrations in 2018 than in 2017 with mean concentrations of 543 ng/g ww and 132 ng/g ww in red fox liver in 2017 and 2018, respectively. The highest concentration of bromadiolone detected in 2018 was 3473 ng/g ww, and was found in red fox liver.
Phenols; were detected in the earthworm samples, and only sporadically detected in the other samples. Bisphenol-A dominated in the few samples of earthworm (64-76 ng/g ww), red fox (41-55 ng/g ww) and brown rat liver (124 ng/g ww) where phenols were detected.
Dominant pollutant groups in each matrix
The median of sum concentrations of the dominant pollutant group for each matrix in the investigated species in 2018 is given below. Note that pesticides were only measured in sparrowhawk eggs. SumToxicMetals is the sum of Hg, Cd, Pb and As.
- Air : SumSiloxanes >> SumCPs > SumOPFRs >sumPCBs - Soil : SumToxicMetals >> SumCPs >> SumOPFR> SumUVcomp.
- Earthworm : SumToxicMetals >> SumPhenols~ SumCPs > SumPFAS - Fieldfare egg : SumPFAS > SumCPs >SumPCBs~ SumToxicMetals - Sparrowhawk egg : SumDDT >> SumCPs ~ SumPCBs > SumPFAS
- Red fox liver : SumToxicMetals ~ SumBiocides > SumCPs > SumPFAS - Brown rat liver : SumToxicMetals >> SumBiocides > SumCPs ~ SumPFAS - Badger liver : SumToxicMetals > SumBiocides > SumCPs > SumPFAS
Trophic magnification factors (TMFs): The typical hydrophobic and well known POPs such as PCBs and PBDEs were found to have TMF values well above 1, indicating a high potential for biomagnification in the food chain earthworm-fieldfare-sparrowhawk. The perfluorinated substance, PFTriA, had a TMF of 2.6, and the TMF for PFOS was 1.8 was slightly higher than in previous years.
Sammendrag
På oppdrag fra Miljødirektoratet analyserte NILU (Norsk institutt for luftforskning), i
samarbeid med Norsk institutt for naturforskning (NINA) og Norsk institutt for vannforskning (NIVA) en lang rekke uorganiske og organiske miljøgifter i luft, jord og dyrearter fra bynært og terrestrisk miljø.
Prosjektet hadde følgende delmål:
- Rapportere konsentrasjoner av utvalgte miljøgifter på flere trofiske nivå av et terrestrisk næringsnett.
- Sammenstille og vurdere fordeling av miljøgiftklassene på tvers av prøver og arter - Vurdere biomagnifiseringspotensialet av miljøgifter ved bruk av næringskjedetilnærming Denne rapporten presenterer funnene fra det sjette året av det urbane terrestriske
programmet. Prøver fra denne overvåkingsperioden ble samlet inn i 2018.
Et stort spekter av kjemiske stoffer ble analysert; persistente organiske miljøgifter, bisfenoler, biocider, pesticider, UV forbindelser, regulerte og nye PFAS stoffer, siloksaner, klorerte paraffiner, organiske fosforflammehemmere og metaller i de ulike prøvene. For hver stoffgruppe ble forurensingsnivåene sammenlignet på tvers av arter og prøver. I tillegg er det vurdert hvilke stoffgrupper som dominerte i de ulike prøvene og artene. Potensialet for biomagnifisering ble også undersøkt.
Under følger en kort oppsummering for hver komponentgruppe som ble analysert i prøvene.
Der sammenligning er gjort mellom artene og ulike organer så er konsentrasjoner av hydrofobe miljøgifter normalisert til fettvekt (fv).
Metaller: I samsvar med tidligere års resultater i overvåkingsprogrammet så var metallkonsentrasjonene høyest i jord. Av de biologiske prøvene inneholdt meitemark, brunrotte og grevling de høyeste konsentrasjonene av tungmetallene Hg, Cd, Pb og As. Som i 2016 og 2017, hadde samleprøven bestående av to gråtrostegg fra et reir ved Kjelsås høyere Pb-konsentrasjon (136 ng/g vv) enn egg fra andre lokaliteter, mer enn 10-20 ganger høyere.
En generell terskelverdi for fysiologisk skadevirkning er satt til ca. 400 ng/g vv i fugleblod.
Konsentrasjon i fugleblod er ikke direkte sammenlignbar med fugleegg, men ingen gråtrostegg hadde konsentrasjon opp mot denne terskelverdien i 2018. Median Hg konsentrasjonen var høyest i meitemark og rødrev på 143 og 110 ng/g vv. En rotteleverprøve hadde en
konsentrasjon av Hg på 1093 ng/g vv. Konsentrasjonen av Cd var høyest i leverprøver av grevling, hvor tre prøver var høyere enn 2000 ng/g vv.
PCB: 2018 data bekreftet tidligere års data at egg fra spurvehauk hadde høyeste median konsentrasjonen av sumPCB med 6974 ng/g fv etterfulgt av gråtrost og rødrev med 784 ng/g fv og 550 ng/g fv. En spurvehaukprøve hadde en sumPCB-verdi på 1874 ng/g vv. Selv om denne konsentrasjonen er lavere enn en generell NOEL verdi for fugl på 4000 ng/g, så kan en ikke neglisjere potensielle effekter siden følsomheten kan variere mellom fuglearter. PCB-153 dominerte i nesten alle prøvetyper, med unntak av lever fra rødrev hvor PCB-180 dominerte, og luft hvor de mer flyktige PCB 52 og 101 dominerte. Luftkonsentrasjonene fra passive luftprøvetakere av PCB i Slottsparken (0.91 ng/dag) og Alnabru (0.12 ng/dag), var mye høyere
enn de som ble målt på overvåkningsstasjoner i Norge, noe som tyder på at byområdet er en kilde for PCB i luft.
PBDE: Nivåene av PBDEer var lavere i alle miljøprøver sammenlignet med PCB og PFAS, noe som er i overensstemmelse med tidligere års resultater. Spurvehauk hadde høyeste median konsentrasjonen av sumPBDEs (465 ng/g fv) etterfulgt av lever fra brunrotte (224 ng/g fv) og gråtrost (181 ng/g fv). BDE-99, -47, -153 og -100 var de viktigste og hadde størst bidrag til sumPBDE i eggene, men BDE-207 og -209 dominerte i lever fra brunrotte. Den høyeste sum konsentrasjonen i ett spurvehaukegg var 147 ng/g vv (2101 ng/g fv). Denne
sumkonsentrasjonen hos spurvehauk er ti ganger lavere enn terskelverdien for
reproduksjonseffekter hos fiskeørn på 1000 ng/g vv. Det samme egget med høyest sumPBDE hadde også høyest sumPCB verdi. Fra passive luftprøvetakere kunne det detekteres flere PBDE-kongenere i byluft. Høyeste konsentrasjoner av sumPBDE i luft ble observert på Alnabru (0.48 ng/dag) og i Slottsparken (0.23 ng/dag), og som for PCB indikerer dette at byen Oslo er en kilde til PBDE i luft.
Nye BFR: De forskjellige stoffene i denne gruppen ble først og fremst detektert i luft, jord, meitemark og brunrotte. Konsentrasjonene av nye BFR var lavere enn konsentrasjonene av PBDE i luft og spurvehauk, men høyere i de andre prøvene, først og fremst på grunn av relativt høye konsentrasjoner av DBDPE, og delvis BTBPE og PBBZ. Passive luftprøvetakere viste høyeste konsentrasjoner for Alnabru og Slottsparken (0.18 og 0.13 ng/dag).
Høyeste median sumBFR konsentrasjon ble målt i gråtrostegg med 490 ng/g lw. DBDPE hadde høyeste konsentrasjon blant new BFR komponenter, men ble detektert i færre prøver enn BTBPE og PBBZ. En ekstrem konsentrasjon av DBDPE ble påvist i lever fra brunrotte på 940 ng/g vv. Vi har ikke kunnet relatere denne konsentrasjonen til en toksisk effekt av DBDPE.
NOAEL for DBDPE i rotte har blitt bestemt til å være 1 000 mg/kg kroppsvekt/dag.
PFAS: Den dominerende PFAS-forbindelsen var PFOS i alle prøvene, bortsett fra luft der kun PFBS og PFHxS ble påvist. Nivåene av PFOS i meitemark fra Alnabru (69 ng/g vv) i 2018 var mye lavere enn i 2017 (531 ng/g vv). Høye median sum konsentrasjoner av sumPFAS ble påvist i spurvehauk (143 ng/g vv) og gråtrost (99 ng/g vv) egg. Høyeste PFOS konsentrasjon (sum av lineær og forgrenet PFOS) ble påvist i spurvehaukegg med 417 ng/g vv. Denne PFOS-
konsentrasjonen er lavere enn en anbefalt terskelverdi for hekkesuksess for PFOS på 1900 ng/g vv i fugleegg. Som observert i 2016 og 2017 for gråtrostegg, hadde prøven fra Grønmo den høyeste PFOS konsentrasjonen på 250 ng/g vv, ti ganger høyere enn gjennomsnitts- konsentrasjonene av de resterende ni prøvene. Gråtrostegg fra Holmenkollen hadde enda høyere sumPFAS-konsentrasjon enn egget fra Grønmo på grunn av høy konsentrasjon av langkjedete perfluorerte karboksylater hvor PFTeA-konsentrasjonen var 137 ng/g vv. Blant nye PFAS forbindelser (6:2 FTS, 8:2 FTS, 10:2 FTS, Cl-PFOS, Cl-PFOA and PFECHS), ble PFECHS funnet i alle ni spurvehaukeggene og en leverprøve fra rotte med relativt lave
konsentrasjoner. Høyeste konsentrasjon av PFECHS i spurvehaukegg var 2.4 ng/g vv.
Forbindelsene 8:2 FTS og 10:2 FTS ble detektert i alle eggene fra gråtrost og spurvehauk. 10:2 FTS ble også detektert i grevling og rottelever. 6:2 FTS og 8:2 FTS ble påvist i noen prøver av rottelever. Høyeste detekterte konsentrasjon av de nye PFAS var 11.8 ng/g vv for 10:2 FTS i gråtrostegg. Cl-PFOS ble kun detektert i en leverprøve fra rotte, 1.2 ng/g vv.
SCCPs/ MCCPs: Klorerte paraffiner (CPs) ble funnet i de fleste prøvene. Gråtrostegg hadde laveste deteksjon der SCCPs og MCCPs ble detektert i henholdsvis 50 og 80 % av prøvene. En prøve av spurvehauk og en prøve fra gråtrost hadde ekstremt høye konsentrasjoner av SCCPs og MCCPs. Gråtrostegg fra Bøler hadde høyeste konsentrasjon med sumCPs verdi på 6850 ng/g vv. Gråstrostegg fra samme lokalitet hadde også høyeste sumkonsentrasjon i 2017. SCCPs dominerte summen for begge årene. Den ekstreme konsentrasjonen av sumCPs i
spurvehaukegg var 9722 ng/g vv hvor MCCPs dominerte summen med 6697 ng/g vv. Det er ikke kjent om disse konsentrasjonene kan utgjøre en risiko for spurvehauk og gråtrost. De estimerte konsentrasjonene av klorparafiner i luft målt i Slottsparken og VEAS var omtrent ti ganger høyere enn de som ble observert på bakgrunnsstasjoner i Norge.
Sykliske siloksaner (cVMS): Luftprøvene hadde høye nivåer av forbindelsene D4, D5 og D6.
Høyeste sum konsentrasjon på 51 ng/dag ble funnet i Slottsparken. Konsentrasjonene av D5 og D6 i Slottsparken basert på opptaksrate i passive prøvetakere var 100-1000 ganger høyere enn data fra bakgrunnsstasjoner i Norge, og reflekterer utslippskilder av siloksaner i
byområdet. I jord og biotaprøvene var siloksanene sporadisk detektert. Basert på PNEC så var ikke nivåene av D4, D5 og D6 i meitemark og gråtrostegg som byttedyr høye nok til å utgjøre noen risiko for rovdyr.
OPFRs: Som med siloksaner hadde luftprøver store mengder OPFR med sumOPFR som varierte fra 1.04 til 6.82 ng/dag. Som i 2017 så var TCPP den dominerende forbindelsen, og i likhet med siloksaner ble den høyeste konsentrasjonen av TCPP og sumOPFR målt i Slottsparken og Alnabru. For biologiske prøver ble OPFRs først og fremst detektert i en samleprøve av jord (sumOPFR på 10.6 ng/g dw) og meitemark (14.4 ng/g vv) og tre samleprøver av brunrotte (1.8-112 ng/g vv). EHDP (95.6 ng/g vv) hadde største bidrag til maksimum sumOPFR i rotter på 112 ng/g vv.
Dekloraner; ble analysert i meitemark, gråtrost, spurvehauk og rødrev. Dekloraner ble kun påvist i noen prøver av meitemark, men Dec-602, Dec-603 og anti-DP ble detektert i mange av de andre organismene, men i relativt lave nivåer sammenlignet med de andre komponent- gruppene i dette programmet. Dec-603 dominerte i gråstrostegg (<LOD-2.23 ng/g vv) og spurvehaukegg (0.37-4.62 ng/g vv), og ble funnet i hhv. 90 % og 100 % av prøvene. I lever fra rødrev hadde anti-DP høyeste konsentrasjon, men ble kun detektert i 50 % av prøvene. Den høyeste median sumkonsentrasjonen av dekloraner ble funnet i spurvehaukegg etterfulgt av gråtrostegg og var på hhv 72 ng/g fv (2.9 ng/g vv) og 33 ng/g fv (1.6 ng/g vv). Vi har ikke kunnet relatere disse nivåene til noen effekter av dekloraner.
Plantevernmidler; ble bare analysert i spurvehaukegg og median konsentrasjon av SumDDT målt i 2018 var 1222 ng/g vv. P,p’-DDE dominerte sumDDT med en mediankonsentrasjon på 1210 ng/g vv. Denne konsentrasjonen er høyere enn en rapportert PNEC på 870 ng/g vv assosiert med 20% eggeskallfortynning i fiskeørn. Syv av ni egg fra Oslo-området var høyere enn 1000 ng/g vv i 2018, som indikerer en risiko for reproduksjonseffekter av DDT for fugl som lever i dette urbane området.
UV-forbindelser; ble detektert i noen av de samleprøvene. UV-327, UV-328 og OC ble detektert i de tre samleprøvene av spurvehauk. UV-328 var den dominerende forbindelsen i leverprøvene (rev, rotte og grevling), mens OC hadde den høyeste konsentrasjonen i en samleprøve av jord, og var den eneste forbindelsen detektert i samleprøven av meitemark.
Høyeste sumkonsentrasjon ble funnet i den ene samleprøven av meitemark og i lever av brunrotte. Effektnivåer for UV-forbindelser er ikke funnet for terrestriske økosystemer.
Biocider (rodenticider); ble målt i rev-, grevling- og rottelever. Forbindelsene ble først og fremst påvist i rødrevlever hvor bromadiolon og brodifacoum dominerte. Bare bromadiolon ble påvist i rottelever ved lavere konsentrasjoner sammenlignet med rødrev. Bromadiolon og brodifacoum var generelt i lavere konsentrasjoner i år sammenlignet med 2017,
gjennomsnittlig verdi på 543 ng/g vv og 132 ng/g vv i rødrevlever. Maksimum konsentrasjon av bromadiolon var 3473 ng/g vv, og ble funnet i lever fra rødrev.
Fenoler; ble detektert i tre analyserte meitemarkprøver, og ble bare sporadisk detektert i de andre artene. Bisfenol-A dominerte i prøvene av meitemark (64-76 ng/g vv), rødrev (41-55 ng/g vv) og brunrotte (124 ng/g vv) hvor fenoler ble detektert.
Dominerende stoffgrupper i de ulike miljøprøvene
Median av sumkonsentrasjoner av de mest dominerende miljøgiftgruppene i de ulike miljøprøvene i 2018 er vist nedenfor. Pesticider ble bare analysert i spurvehauk og SumToxicMetals er summen av konsentrasjonene av Hg, Cd, Pb og As.
- Luft : SumSiloxanes >> SumCPs > SumOPFRs >SumPCBs - Jord : SumToxicMetals >> SumCPs >> SumOPFR> SumUVcomp.
- Meitemark : SumToxicMetals >> SumPhenols~ SumCPs> SumPFAS - Gråtrost egg : SumPFAS > SumCPs >SumPCBs~ SumToxicMetals - Spurvehauk egg : SumDDT >> SumCPs ~ SumPCBs > SumPFAS
- Rødrev lever : SumToxicMetals ~ SumBiocides > SumCPs> SumPFAS - Brunrotte lever : SumToxicMetals >> SumBiocides > SumCPs > SumPFAS - Grevling lever : SumToxicMetals >> SumBiocides > SumCPs~ SumPFAS
TMF: De typiske hydrofobe og velkjente POPene som PCB og PBDE hadde TMF godt over 1, som indikerte høyt potensial for magnifisering i næringskjeden meitemark-gråtrost-
spurvehauk. Den perfluorerte substansen PFTRiA hadde en TMF på 2.6 og PFOS var noe høyere enn tidligere år med 1.8.
Abbreviations
BAF Bioaccumulation factor
BFR brominated flame retardants
CI confidence interval
dw dry weight
EI electron impact ionization
ESI electrospray ionization
ww wet weight
vv våtvekt
GC-HRMS gas chromatography – high resolution mass spectrometry
GC-MS gas chromatography – mass spectrometry
ICP MS inductive coupled plasma – mass spectrometry
LC-MS liquid chromatography – mass spectrometry
LOD limit of detection
lw lipid weight
fv fettvekt
LOEL lowest observed effect level
MEC measured environmental concentration
M-W U Mann–Whitney U test
MCCP medium-chain chlorinated paraffins
N detected/measured samples
n.a. not analysed
NCI negative chemical ionization
NOEC no observed effect concentration
NOAEL no observed adverse level
NOEL no observed effect level
n-PFAS neutral polyfluorinated compounds
newPFAS new polyfluorinated compounds
NP-detector nitrogen-phosphorous detector
PBDE polybrominated diphenylethers
PCA principal component analysis
PCB polychlorinated biphenyls
PCI positive chemical ionization
PEC predicted environmental concentration
PFAS perfluorinated alkylated substances
PNEC predicted no effect concentration
PSA primary/secondary amine phase
SCCPs short-chain chlorinated paraffins
SSD species sensitivity distribution
SIR selective ion reaction
SPE solid phase extraction
TL Trophic level
TMF Trophic magnification factor
UHPLC ultra high pressure liquid chromatography
Content
Summary... 2
Sammendrag ... 6
Abbreviations ... 10
1.Introduction ... 15
1.1 Background and objectives ... 15
1.2 Investigated samples ... 15
1.3 Investigated pollutants ... 17
1.3.1 Metals including Hg ... 20
1.3.2 Polychlorinated biphenyls (PCB) ... 20
1.3.3 Polybrominated diphenylethers (PBDEs) ... 20
1.3.4 Per- and polyfluorinated alkyl substances (PFAS) ... 21
1.3.5 Cyclic volatile methyl siloxanes, (cVMS) ... 22
1.3.6 Chlorinated paraffins (CPs) ... 22
1.3.7 Organophosphorous flame retardants (OPFR) ... 23
1.3.8 Dechloranes ... 24
1.3.9 Alkylphenols and bisphenols ... 24
1.3.10UV compounds ... 25
1.3.11Biocides ... 26
1.3.12Stable isotopes ... 27
2.Methods ... 28
2.1 Sampling ... 28
2.2 Sample preparation and analysis ... 34
2.3 Biomagnification ... 37
2.4 Statistical methods ... 38
3.Results ... 39
3.1 PCBs ... 42
3.1.1 Air ... 42
3.1.2 Soil ... 42
3.1.3 Earthworms ... 42
3.1.4 Fieldfare ... 43
3.1.5 Sparrowhawk ... 43
3.1.6 Brown Rats ... 44
3.1.7 Red fox ... 44
3.1.8 Badger ... 44
3.1.9 Summary of PCB results ... 45
3.2 PBDEs and new BFR ... 47
3.2.1 Air ... 47
3.2.2 Soil and earthworm samples ... 47
3.2.3 Fieldfare ... 47
3.2.4 Sparrowhawk ... 48
3.2.5 Brown rat ... 49
3.2.6 Red fox ... 49
3.2.7 Badger ... 49
3.2.8 Summary PBDEs and new BFR ... 49
3.3 Per- and polyfluoroalkyl substances (PFASs) ... 52
3.3.1 Air ... 53
3.3.2 Soil ... 53
3.3.3 Earthworms ... 54
3.3.4 Fieldfare ... 54
3.3.5 Sparrowhawk ... 54
3.3.6 Brown rat ... 55
3.3.7 Red fox ... 55
3.3.8 Badger ... 55
3.3.9 Bumblebees ... 55
3.3.10Summary PFAS ... 56
3.4 Metals ... 59
3.4.1 Soil ... 59
3.4.2 Earthworm ... 59
3.4.3 Fieldfare ... 60
3.4.4 Sparrowhawk ... 60
3.4.5 Brown rat ... 61
3.4.6 Red fox ... 61
3.4.7 Badger ... 62
3.4.8 Summary metals ... 62
3.5 Chlorinated paraffins (CPs) ... 64
3.5.1 Air ... 64
3.5.2 Soil ... 64
3.5.3 Earthworms ... 64
3.5.4 Fieldfare ... 65
3.5.5 Sparrowhawk ... 65
3.5.6 Brown Rats ... 65
3.5.7 Red fox ... 66
3.5.8 Badger ... 66
3.5.9 Summary S/MCCPs ... 66
3.6 Cyclic Siloxanes ... 67
3.6.1 Air ... 68
3.6.2 Soil and earthworm ... 68
3.6.3 Fieldfare ... 68
3.6.4 Sparrowhawk ... 69
3.6.5 Brown Rat ... 69
3.6.6 Red fox ... 69
3.6.7 Badger ... 69
3.6.8 Summary cyclic siloxanes ... 69
3.7 Organic phosphorous flame retardants (OPFR)... 70
3.7.1 Air ... 70
3.7.2 Soil ... 71
3.7.3 Earthworms ... 71
3.7.4 Fieldfare ... 72
3.7.5 Sparrowhawk ... 72
3.7.6 Brown Rat ... 72
3.7.7 Red fox ... 72
3.7.8 Badger ... 72
3.7.9 Summary OPFRs ... 72
3.8 Dechloranes ... 74
3.8.1 Earthworm ... 74
3.8.2 Fieldfare ... 74
3.8.3 Sparrowhawk ... 74
3.8.4 Red fox ... 75
3.8.5 Summary dechloranes ... 75
3.9 Phenolic compounds and alkyl ethoxilates ... 77
3.9.1 Earthworms ... 77
3.9.2 Red fox ... 77
3.9.3 Brown rats ... 77
3.9.4 Summary phenols ... 77
3.10UV compounds ... 78
3.11Biocides ... 78
3.11.1Red fox ... 78
3.11.2Brown rats ... 79
3.11.3Badger ... 79
3.11.4Summary biocides ... 79
3.12Pesticides ... 80
3.12.1Summary pesticides ... 83
3.13Compound classes across air, soil and species ... 84
3.14Bioaccumulation and biomagnification ... 91
3.14.1Results from stable nitrogen and carbon isotope analyses... 92
3.14.2Estimation of biomagnification by calculation of TMF values ... 97
3.15Changes over time of pollution loads ... 102
4.Conclusion and Recommendations... 104
5.Acknowledgements ... 106
6.References ... 107
Attachments:
Appendix 1: Concentrations of pollutants in individual samples 2018 Appendix 2: GPS coordinates for sampling locations 2018
Appendix 3: Eggshell data in sparrowhawks from the Oslo area 2018 Appendix 4: Pathology studies of red foxes and brown rats 2018
1. Introduction
1.1 Background and objectives
The main objective of this monitoring study was to investigate the concentrations of selected organic and inorganic pollutants and their bioaccumulation potential and possible adverse effects in species living in a terrestrial and urban ecosystem. The urban sites in or in the near vicinity of Oslo were identified for sampling. The results from this study will feed into the evaluation of potential environmental hazards and ongoing regulatory work, at both national- and
international level. The project had the following key goals:
Report concentrations of chosen environmental pollutants in several trophic levels of the terrestrial food chain
Evaluate the bioaccumulation potential of pollutants in the terrestrial food chain
Evaluate the total exposure in terrestrial animals
Evaluate how land-living species are exposed to a variety of pollutants
Evaluate trends in various pollutants over time
1.2 Investigated samples
Sparrowhawk (Accipiter nisus).
The sparrowhawk is a small bird of prey with a widespread distribution in Norway. It feeds mainly on birds of small to medium size, and thrushes (Turdidae) are preferred prey (Haftorn 1971, Hagen 1952). It commonly occurs close to human habitations, where it can breed in different types of forest patches. Most of the population migrates to south-western Europe during winter, but some individuals stay, and often feed on small garden birds during winter (Haftorn 1971). The sparrowhawk is on top of a terrestrial food-chain (invertebrates-small birds- sparrowhawk) and is therefore subjected to bioaccumulation of persistent organic pollutants (POPs). The sparrowhawk is a protected species in Norway, so the collection of eggs for analysis was carried out under a special license issued by the Norwegian Environment Agency. The
species nests in stick-nests in forests or forest patches and lays 4-6 eggs. It has been documented that the sparrowhawk is one of the species most affected by environmental pollutants in Europe after World War II (Bennington 1971, Bennington 1974, Burgers et al. 1986, Cooke 1979, Newton
& Bogan 1978, Newton et al. 1986, Ratcliffe 1960), and also in Norway (Bühler & Norheim 1981, Frøslie et al. 1986, Holt & Sakshaug 1968, Nygård et al. 2006, Nygård & Polder 2012). Estimated trophic level 4.
Fieldfare (Turdus pilaris)
The fieldfare is a member of the thrush family and is a common breeding bird in Eurasia. It is a migratory species; birds that breed in the northern regions migrate to the south and south-west in the winter. The majority of the birds that breed in Norway spend the winter months in south- west Europe (Bakken et al. 2006). It is omnivorous, with its diet mainly consisting of
invertebrates during spring and summer, especially earthworms. The diet changes more to berries, grain and seeds during autumn and winter (Haftorn 1971). Estimated trophic level 3.
Earthworms (Lumbricidae)
Earthworms are animals commonly living in soil feeding on live and dead organic matter. Its digestive system runs through the length of its body. It conducts respiration through its skin. An earthworm has a double transport system composed of coelomic fluid that moves within the fluid-filled coelom and a simple, closed blood circulatory system. Earthworms are
hermaphrodites, having both male and female sexual organs. Earthworms form the base of many food chains. They are preyed upon by many species of birds (e.g. starlings, thrushes, gulls, crows), mammals (e.g. bears, badgers, foxes, hedgehogs), and invertebrates (e.g. ground beetles, snails). They are found almost anywhere in soil that contains some moisture (Macdonald 1983). Lumbricus terrestrisk was the most common species in the samples. Estimated trophic level 2 (Hui et al. 2012). Sampling sites for earthworm were Alnabru, Slottsparken, Fornebu, VEAS, and Frognerseteren.
European Badger (Meles meles)
The European badger is a predator and is the second largest member of the family Mustelidae, next to the wolverine. It can be up to 80 cm in length and up to 16 kg during the autumn when it has plenty of food. The most important food item is earthworm, but it is an opportunistic feeder.
The badger can be found in Østlandet and Sørlandet and up to Trøndelag in Norway, and also detected in southern part of Nordland county. It is not an uncommon inhabitor in more populated areas and cities. Estimated trophic level: 3
Red fox (Vulpes vulpes)
The red fox is the most abundant carnivore in Europe and is widespread. It is found over most of the world. It inhabits most of Norway, from the mountains, through the forests and the
agricultural landscape and is also found in the cities. It primarily feeds on rodents, but it is a generalist predator feeding on everything from small ungulate calves, hares, game-birds and other birds, reptiles and invertebrates, to human offal. Estimated trophic level 3-4.
Brown rat (Rattus norvegicus)
The brown rat is one of the most common rats in Europe. This rodent can become up to 25 cm long. The brown rat can be found wherever humans are living, particularly in urban areas. It is a true omnivore, feeding on everything from bird eggs to earthworms and human waste. The brown rat breeds throughout the whole year, producing up to 5 litters a year. Estimated trophic level: 3-4.
Bumblebees (Bombus)
For the first time in the monitoring program, bumblebee samples were available for PFAS analysis in 2018. The sampling of bumblebees were from three locations, two locations Frognerseteren and Sognsvann in Oslo area, and Hvasser, Vestfold as a reference area.
Bumblebees is common in Norway and may be seen as a link from soil/plant system to some of the bird species. Several species are common in Norway.
Soil
Soil samples were taken from the surface layer (0-20 cm), combining three subsamples to one combined sample per location. The locations for soil samples were the same locations as for the earthworm samplings to make direct comparisons possible.
Air
For the third time in the urban terrestrial program, air samples were collected using passive air samplers (PAS) at the five locations chosen for soil- and earthworm sampling (Alnabru,
Slottsparken, Grønmo, VEAS, and Frognerseteren). Two types of PAS adsorbents were used at all sites: i) polyurethane foam (PUF), and ii) polystyrene-divinylbenzene copolymeric resin (XAD).
The PAS were deployed over a period of three months (late June/early July to October 2018) giving time-weighted mean concentration over that time period.
1.3 Investigated pollutants
In this study a total of 138 compounds were investigated. These included nine metals, seven PCBs, 40 PFAS, 13 PBDEs, new BFRs, three siloxanes (D4, D5 and D6), chlorinated paraffins (SCCPs and MCCPs), organic phosphorous compounds (OPFRs), UV compounds, biocides and phenolic compounds, together with the stable isotopes δ15N, δ13C and δ34S. Some pesticides (DDT and its breakdown products, HCB and HCH isomers) were analysed in sparrowhawk eggs. OPFR and UV compounds were measured in a selection of pooled samples, representing the species covered within the project. An overview over the analysed compounds is given in Table 1 Table 1: Overview over analysed compounds.
Parameters Abbreviation CAS number
Metals
Chromium Cr 7440-47-3
Nickel Ni 7440-02-0
Copper Cu 7440-50-8
Zinc Zn 7440-66-6
Arsenic As 7440-38-2
Silver Ag 7440-22-4
Cadmium Cd 7440-43-9
Lead Pb 7439-92-1
Total-Mercury Hg 7440-02-0
Polychlorinated biphenyls (PCB)
2,4,4'-Trichlorobiphenyl 28 PCB-28 7012-37-5
2,2',5,5'-Tetrachlorobiphenyl 52 PCB-52 35693-99-3
2,2',4,5,5'-Pentachlorobiphenyl 101 PCB-101 37680-73-2
2,3',4,4',5-Pentachlorobiphenyl 118 PCB-118 31508-00-6
2,2',3,4,4',5'-Hexachlorobiphenyl 138 PCB-138 35065-28-2
2,2',4,4',5,5'-Hexachlorobiphenyl 153 PCB-153 35065-27-1
2,2',3,4,4',5,5'-Heptachlorobiphenyl 180 PCB-180 35065-29-3
Per- and polyfluorinated alkyl substances (PFAS)
PFCA (perfluorinated carboxylate acids)
Perfluorinated butanoic acid PFBA 307-24-4
Perfluorinated hexanoic acid PFHxA 375-85-9
Perfluorinated heptanoic acid PFHpA 335-67-1
Perfluorinated octanoic acid PFOA 375-95-1
Perfluorinated nonanoic acid PFNA 335-76-2
Perfluorinated decanoic acid PFDcA 2058-94-8
Perfluorinated undecanoic acid PFUnA 307-55-1
Perfluorinated dodecanoic acid PFDoA 72629-94-8
Perfluorinated tridecanoic acid PFTriA 376-06-7
Perfluorinated tetradecanoic acid PFTeA 67905-19-5
Perfluorinated hexadecanoic acid PFHxDA 16517-11-6
Perfluorinated octadecanoic acid PFOcDA 375-73-5 PFSA (Perfluorinated sulfonates)
Perfluorinated butane sulfonate PFBS
Perfluorinated pentane sulfonate PFPS 2706-91-4
Perfluorinated hexane sulfonate PFHxS 355-46-4
Perfluorinated heptane sulfonate PFHpS 375-92-8
Perfluorinated octane sulfonate
Perfluorinated octane sulfonate (branched) PFOS
brPFOS 2795-39-3
Perfluorinated nonane sulfonate PFNS 17202-41-4
Perfluorinated decane sulfonate Perfluoroundecane sulfonate Perfluorododecane sulfonate Perfluorotridecane sulfonate Perfluorotetradecane sulfonate
PFDcS PFUnS PFDoS PFTrS PFTS
67906-42-7
nPFAS (polyfluorinated neutral compounds) Perfluorooctane sulfonamide
N-Methyl perfluorooctane sulphonamide N-Ethyl perfluorooctane sulfonamide
N-Methyl perfluorooctane sulfonamidoethanol N-Ethyl perfluorooctane sulfonamidoethanol
6:2-Fluorotelomer alcohol 8:2-Fluorotelomer alcohol 10:2-Fluorotelomer alcohol 12:2-Fluorotelomer alcohol
PFOSA meFOSA etFOSA meFOSE etFOSE 6:2 FTOH 8:2 FTOH 10:2 FTOH 12:2 FTOH
754-91-6 31506-32-8 4151-50-2 24448-09-7 1691-99-2 647-42-7 678-39-7 865-86-1 39239-77-5 New PFAS
6:2 Fluortelomersulphonate 8:2 Fluortelomersulphonate 10:2 Fluortelomersulphonate
dodecafluorohexyloxy)- 1,1,2,2-tetrafluoroethane sulfonate Monochlorinated PFOS
Monochlorinated PFOA Cyclohexanesulfonic acid
6:2 FTS 8:2 FTS 10:2 FTS Cl-PFOS Cl-PFOA PFECHS
27619-97-2 481071-78-7
777011-38-8 335-63-7 67584-42-3
Polybrominated diphenylethers (PBDE)
2,2',4,4'-Tetrabromodiphenylether 47 BDE-47 5436-43-1
2,2',4,4',5-Pentabromodiphenylether 99 BDE-99 60348-60-9
2,2',4,4',6-Pentabromodiphenylether 100 BDE-100 189084-64-8
3,3',4,4',5-Pentabromodiphenylether 126 BDE-126 366791-32-4
2,2',4,4',5,5'-Hexabromodiphenylether 153 BDE-153 68631-49-2
2,2',4,4',5,6'-Hexabromodiphenylether 154 BDE-154 207122-15-4
2,2’,3,3’,4,5’,6-Heptabromodiphenylether 175 BDE-175 446255-22-7 2,2',3,4,4',5',6-Heptabromodiphenylether 183 BDE-183 207122-16-5 2,3,3’,4,4’,5,6- Heptabromodiphenylether 190 BDE-190 189084-68-2 2,2',3,3',4,4',5,6'-Octabromodiphenylether196 BDE-196 446255-38-5 2,2’,3,3’,5,5’6,6’-Octabromodiphenylether 202 BDE-202 67797-09-5 2,2',3,3',4,4',5,5',6-Nonabromdiphenylether 206 BDE-206 63936-56-1 2,2’,3,3’4,4’,5,6,6’-Nonabromodiphenylether 207 BDE-207 437701-79-6 Decabromodiphenylether 209
New BFR
Decabromodiphenyl ethane 2,4,6-tribromophenyl ether)
α-1,2-Dibromo-4-(1,2-di-bromo-ethyl)cyclohexane β-1,2-Dibromo-4-(1,2-di-bromo-ethyl)cyclohexane γ/δ- 1,2-Dibromo-4-(1,2-di-bromo-ethyl)cyclohexane 2-bromoallyl 2,4,6-tribromophenyl ether
1,2,3,4,5 Pentabromobenzene Pentabromotoluene
Pentabromoethylbenzene Hexabromobenzene
2,3-dibromopropyl 2,4,6-tribromophenyl ether 2-Ethylhexyl 2,3,4,5-tetrabromobenzoate 1,2-Bis(2,4,6-tribromophenoxy)ethane
BDE-209 DBDPE ATE (TBP-AE) α-TBECH β-TBECH γ/δ-TBECH BATE PBBZ PBT PBEB HBB DPTE EHTBB BTBPE
1163-19-5 84852-53-9 3278-89-5 3322-93-8
99717-56-3 608-90-2 87-83-2 85-22-3 87-82-1 35109-60-5 183658-27-7 37853-59-1
2,3,4,5-tetrabromophthalate Dechloranes
Dechlorane plus Dechlorane plus syn Dechlorane plus anti Dechlorane 601 Dechlorane 602 Dechlorane 603 Dechlorane 604 Dibromo-aldrin
TBPH (BEH /TBP) DP
syn-DP anti-DP Dec-601 Dec-602 Dec-603 Dec-604 DBA
26040-51-7 13560-89-9 135821-03-3 135821-74-8 3560-90-2 31107-44-5 13560-92-4 34571-16-9 20389-65-5
Cyclic volatile methyl siloxanes D4 556-67-2
D5 541-02-6
D6 540-97-6
Chlorinated paraffins
Short-chain chlorinated paraffins (C10-C13) SCCPs 85535-84-8
Medium-chain chlorinated paraffins (C14-C17) MCCPs 85535-85-9 Organic phosphorous flame retardants (OPFR)
Tri(2-chloroethyl)phosphate Tris(2-chloroisopropyl) phosphate Tris(1,3-dichloro-2-propyl)phosphate
TCEP TCPP/TCIPP TDCPP/TDCIPP
115-96-8 13674-84-5 13674-87-8 Tris(2-butoxyethyl) phosphate
2-etylhexyldiphenyl phosphate Tricresyl phosphate
Tri-n-butylphosphate Tri-iso-butylphosphate Triethyl phosphate
Tripropyl phosphate Triisobutyl phosphate
Butyl diphenyl phosphate Triphenyl phosphate Dibutylphenyl phosphate Trixylylphosphate
Tris(4-isopropylphenyl)phosphate Tris(4-Tert-butylphenyl)phosphate Tris(2-ethylhexyl)phosphate
TBEP/TBOEP EHDP/EHDPP TCP
TBP/ TnBP TBP/TiBP TEP TPrP/TPP TiBP BdPhP TPP/TPhP DBPhP TXP TIPPP/T4IPP TTBPP TEHP
78-51-3 1241-94-7 1330-78-5 126-73-8 126-71-6 78-40-0 513-08-6 126-71-6 2752-95-6 115-86-6 2528-36-1 25155-23-1 26967-76-0 78-33-1 78-42-2 UV compounds
Octocrylen Benzophenone-3
Ethylhexylmethoxycinnamate UV-327
UV-328 UV-329
OC BP3 EHMC UV-327 UV-328 UV-329
6197-30-4 131-57-7 5466-77-3 3864-99-1 25973-55-1 3147-75-9 Biocides (Rodenticides)
Bromadiolon Brodifacoum Flocumafen Difenacoum
28772-56-7 56073-10-0 90035-08-8 56073-07-5 Phenols
Bisphenol A Bisphenol S Bisphenol F 4-n-Nonylphenol 4-n-Octylphenol 4-t-Octylphenol Tetrabromobisphenol A
Bis-A Bis-S Bis-F 4n-nonyl 4n-octyl 4t-octyl TBBPA
80-05-7 80-09-1 620-92-8 104-40-5 1806-26-4 140-66-9 79-94-7 Pesticides
Hexachlorobenzene α-hexachlorohexane β-hexachlorohexane γ-hexachlorohexane
1,1,1-Trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)ethane 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene 2,2-(2-Chlorophenyl-4'-chlorophenyl)-1,1-dichloroethene 1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene
HCB α-HCH β-HCH γ-HCH o,p’-DDT p,p’-DDT o,p’-DDE p,p’-DDE
118-74-1 319-84-6 319-85-7 58-89-9 789-02-6 50-29-3 3424-82-6 72-55-9
Metals including Hg
Because of their high degree of toxicity, even at low concentrations, mercury (Hg), lead (Pb) cadmium (Cd) and arsenic (As) are considered priority metals that are of environmental and public health concern (Tchounwou et al. 2012; AMAP, 2009). This group is therefore of main focus in this report and defined as the group ‘toxic metals’. These metallic elements are considered systemic toxicants that are known to induce multiple organ damage, even at lower levels of exposure. Best studied is the uptake of metals from soil to invertebrates (Heikens et al.
2001). The impact these metals have on humans and animals is well known, and all four metals are considered as environmentally hazardous compounds (Latif et al. 2013). Recently, there has been an increased use of silver as nanoparticles. Nanotechnology makes it possible to combine silver (Ag) with other materials, such as different polymers. As a result, Ag now can be found in a variety of new products, which again lead to alteration of emission sources and patterns.
Adsorbed Ag may have long residence time in the organism (Rungby 1990). Arsenic is also known as a toxic metalloid (Klaassen 2008). Among the different metals determined in the present work, Hg, Pb and Cd have a potential to bioaccumulate (Connell et al. 1984; Latif et al. 2013).
However, Hg (as methyl-mercury (MeHg)) is the only metal with high bioaccumulation potential through food-chains.
Polychlorinated biphenyls (PCB)
Polychlorinated biphenyls (PCBs) have been used in a variety of industrial applications since the 1930s. PCBs were used in Norway until the 1980s, in cooling agents and insulation fluids, as plasticizers, lubricant oils, hydraulic fluids and sealants among others. Use of PCBs was banned in Norway in 1980. They are known to degrade very slowly in the environment, are toxic, may bioaccumulate and undergo long-range environmental transport (Gai, et al. 2014). As a result, PCBs are recognized as persistent organic pollutants (POPs) and are regulated under the Stockholm Convention and the convention on long-range transboundary air pollution (CLRTAP).
They are widely distributed in the environment and can be found in air, water, sediments and biota. Most PCBs are poorly water soluble, but dissolve efficiently in lipid-rich parts of organisms (hydrophobic and lipophilic). They can affect the reproduction success, impair immune response and may cause defects in the genetic material. PCBs can be metabolized in organisms and form metabolites causing hormonal disturbances. This study includes the group of PCBs found to be dominating in most environmental matrices, the non-dioxin like PCBs, the so-called PCB7 group.
Polybrominated diphenylethers (PBDEs)
Polybrominated diphenylethers (PBDEs) is a group of additive flame retardants with a wide variety of uses in plastics/ polymers/composites, textiles, furniture, housings of computers and TVs, wires and cables, pipes and carpets, adhesives, sealants, coatings and inks. There are three commercial PBDE products, technical or commercial penta-, octa- and deca-BDE. These are all technical mixtures containing different PBDE congeners. Tetra-, penta-, hexa- and heptaBDE congeners were listed in the Stockholm Convention and CLRTAP in 2009, due to being persistent, bioaccumulative, and toxic chemicals that can undergo long-range environmental transport (Darnerud, 2003; Law et al., 2014). As a result, the commercial penta- and octa-PBDE mixtures were globally banned. The use of commercial decaBDE was banned in Norway in 2008. In the same year a restriction on the use of commercial decaBDE in electrical and electronic products entered into force in the EU. A restriction on the manufacture, use and placing on the market of decaBDE in EU enter into force in 2019. In North-America voluntary agreements with the industry have led to reduced use of decaBDE. Globally, commercial deca-BDE is still widely used and remains a high production volume chemical. However, an agreement for including decaBDE in the Stockholm Convention as a POP was settled in May, 2017.
The tetra- and pentaBDE congeners BDE 47 and 99, which were the main components of
commercial pentaBDE mixtures, are among the most studied PBDEs. The early documentation of congeners of the technical mixtures penta- and octa-BDE detected in the Arctic was one of the main reasons to ban production, import, export, sales and use of products with more 0.1 % (by weight) of penta-, octa- and deca-BDE in Norway. The regulation and banning of the PBDEs, and most probably better waste handling, have resulted in a decrease of most BDEs, except BDE 209, the main component of commercial deca-BDE, over time (AMAP 2009; Helgason et al. 2009).
Spatial trends of PBDEs in arctic seabirds and marine mammals indicate that Western Europe and eastern North America are important source regions of these compounds via long-range
atmospheric transport and ocean currents. The tetra- to hexa-BDEs biomagnify in arctic food webs while results for the fully brominated PBDE congener, BDE 209 or deca-BDE, are more ambiguous. Several lines of evidence show that also BDE-209 bioaccumulates, at least in some species. The available bioaccumulation data largely reflects species and tissue differences in uptake, metabolism and elimination, as well as differences in exposure and also analytical challenges in measuring BDE-209 correctly. Moreover, in the environment and biota, BDE-209 can debrominate to lower PBDE congeners that are more persistent, bioaccumulative and toxic. PBDE concentrations are often lower in terrestrial organisms compared to marine top predators (de Wit et al. 2010 and references herein).
New brominated flame retardants (New BFR)
As a result of the regulation of the penta- and octa-BDEs and more recently also deca-BDE, new non-PBDE BFRs have been introduced into the market as replacement FRs. For example,
firemaster 550 (containing BEHTBP) is a replacement product for penta-BDE (Venier and Hites, 2008) that was introduced to the market in 2003 (Stapleton et al., 2008). Saytex 8010
(Albemarle) and Firemaster 2100 (Chemtura), which are common trade names for decabromodiphenyl ethane (DBDPE), are replacement products for deca-BDE that were introduced into the market in the mid-1980s (Umweltbundesamt, 2001).
Per- and polyfluorinated alkyl substances (PFAS)
Per- and polyfluorinated alkyl substances (PFASs) have been widely used in many industrial and commercial applications. The chemical and thermal stability of a perfluoroalkyl moiety, caused by a very strong C-F bond, in addition to its hydrophobic and lipophobic nature, lead to highly useful and enduring properties in surfactants and polymers. Polymer applications include textile stain and water repellents, grease-proof, food-contact paper and other food contact materials used for cooking. Surfactant applications that take advantage of the unparalleled aqueous surface tension–lowering properties include processing aids for fluoropolymer manufacture, coatings, and aqueous film–forming foams (AFFFs) used to extinguish fires involving highly flammable liquids. Numerous additional applications have been described, including floor polish, ski waxes, and water-proof coatings of textile fibers (Buck et al 2011). Since they are so
persistent and hardly degrade in the environment, and due to their widespread use, PFASs have been detected worldwide in the environment, wildlife, and humans. Scientific studies focus on how these substances are transported in the environment, and to what extent and how humans and wildlife are exposed and their potential toxic effects (Butt et al. 2010; Jahnke et al. 2007;
Kannan et al. 2005; Stock et al. 2007; Taniyasu et al. 2003; Trier et al. 2011; de Wit et al. 2012).
Studies have revealed the potential for atmospheric long-range transport of PFAS (Ahrens et al, 2011; AMAP Assessment 2015). Toxic effects on biological organisms and humans where for example discussed by Gai et al. (2014), Hagenaars et al. (2008), Halldorsson et al. (2012),
Newsted et al. (2005), and Whitworth et al. (2012). Polyfluorinated acids are structurally similar to natural long-chain fatty acids and may displace them in biochemical processes and at
receptors, such as PPARα and the liver-fatty acid binding protein (L-FABP). Perfluoroalkanoates, particularly PFOA, PFNA and PFDA, but not PFHxA, are highly potent peroxisome proliferators in rodent livers and affect mitochondrial, microsomal, and cytosolic enzymes and proteins involved in lipid metabolism. Beach et al. (2006) reported an increased mortality for birds (mallards Anas platyrhynchos and northern bobwhite quail Colinus virginianus) and a reduced reproduction success have been observed. PFOA and other PFAS are suspected to be endocrine disruptors and exposure during pregnancy has induced both early and later life adverse health outcomes in rodents. Associations between PFOA exposures and human health effects have been reported.
PFOS, its salts and PFOSF are recognized as POPs, and are listed in the Stockholm Convention and CLRTAP. However globally, the production and use of PFOS, its salts and PFOSF is still allowed for certain applications. In Norway, PFOS and PFOA are banned, and the C9-C14 PFCAs and PFHxS1 are on the Norway’s Priority List of Hazardous substances as well as being included in the candidate list of substances of very high concern for Authorization in ECHA.
New PFASs
In addition to the well known PFAS, more than 5000 PFASs are on the global market for intentional uses, and the chemical identities of many are yet unknown (Wang et al., 2017).
Emissions and leakage to the environment are unavoidable, and sooner or later, environmental concentrations will be reported. For example, in a recent study (MacInnis et al 2017) perfluoro- 4-ethylcyclohexane-sulfonate (PFECHS) was detected for the first time in an atmospherically derived sample, and a potential source was attributed to aircraft hydraulic system leakage. Also, Pan reported the occurrence and bioaccumulation of hexafluoropropylene oxide trimer acid in surface water and fish (Pan et al., 2017). Gebbink et al. 2017, published findings of the PFOA replacement chemical GenX at all downstream river sampling sites with the highest
concentration (812 ng/L) at the first sampling location downstream from a production plant in the Netherlands, proving the necessity of measuring for a broad range of emerging PFAS.
Cyclic volatile methyl siloxanes, (cVMS)
There are concerns about the properties and environmental fate of the three most common cVMS; D4, D5, and D6 (Wang et al., 2013). These compounds are used in large volumes in personal care products and technical applications and are released to the environment either through volatilization to air or through wastewater effluents. Once emitted to water, they can sorb to particles and sediments or be taken up by aquatic biota. They are persistent in the environment, can undergo long-range atmospheric transport, and can have high concentrations in aquatic biota, but often lower in the terrestrial environment. There is still limited knowledge on their toxicity, but D4 has been shown to display endrocrine disrupting effects. D4 and D5 are listed on Norway’s priority list with the aim to stop emissions of these substances within 2020.
The European Commission has published its Regulation to restrict the use of
octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in wash-off cosmetic products in a concentration equal to or greater than 0.1% by weight.
Chlorinated paraffins (CPs)
CPs have been produced since the 1930s and the world production of CPs was 300,000 tonnes in 2009. CPs are used in coolants and lubricants in metal manufacturing industry and as plasticizers and flame-retardant additives in plastic, sealants, rubber and leather (KEMI, 2013, WHO 1996).
1 https://echa.europa.eu/documents/10162/40a82ea7-dcd2-5e6f-9bff-6504c7a226c5
The non-flammability of CPs, particularly at high chlorine contents, relies on their ability to release hydrochloric acid at elevated temperatures, thereby inhibiting the radical reactions in flames (WHO, 1996).
There exist some data on SCCPs and MCCPs detected in Norwegian environment and other parts of the world, including Arctic. Air monitoring at Zeppelin observatory, Svalbard, reports air concentrations of sum S/MCCPs around 300 pg/m3. In air collected at Bear Island (Norway), concentrations were 1.8 to 10.6 ng/m3 (Borgen et al. 2003). In a screening study (Harju et al., 2013), SCCPs and MCCPs were detected in Norwegian Arctic biota. Levels of SCCPs were found to dominate compared to MCCPs in polar bear and seal plasma, kittiwake eggs, cod liver and polar cod. However, the opposite trend was observed for glaucous gull plasma and eider duck eggs where MCCPs were found at higher concentrations. The data indicated that SCCPs and MCCPs biomagnified in Arctic food webs with TMF > 1. A recent subtropical marine food web study also indicated that SCCPs and MCCPs biomagnified with trophic magnification factors for ∑SCCPs and
∑MCCPs were 4.29 and 4.79 (Zeng et al 2017). In a Canadian freshwater study in Lake Ontaio and Lake Michigan , SCCPs and MCCPs were found to biomagnify between prey and predators from both lakes with highest values observed for Diporeia-sculpin (Lake Ontario, C15Cl9 = 43; Lake Michigan, C10Cl5 = 26). Trophic magnification factors for the invertebrates−forage fish−lake trout food webs from the same study ranged from 0.41 to 2.4 for SCCPs and from 0.06 to 0.36 for MCCPs (Houde et al., 2008). SCCPs and MCCPs have been found in sediments from landfills in Norway at levels of up to 19,400 and 11,400 ng/g ww with peak levels associated with waste deposition from mechanical and shipping industries (Borgen et al., 2003). CPs have been detected in biota samples collected in Norway, SCCPs ranged from 14 to 130 ng/g wet weight (ww) in mussels and were also detected in moss samples (3–100 ng/g ww), revealing the
potential transportation of SCCPs in the atmosphere (Borgen et al., 2003). In fish livers collected from samples in the North and Baltic Seas, SCCPs and MCCPs ranged from 19 to 286 and <10 to 260 ng/g ww (Geiss et al. 2010; Reth et al. 2006). In a recent study (Yuan & de Wit, 2018), SCCPs and MCCPs were measured in Swedish terrestrial birds and animals; SCCPs and MCCPs
concentrations in starling were 360 and 310 ng/g lw, respectively; in peregrine falcon SCCPs and MCCPs were 580 and 410 ng/g lw. Bank vole had 420 and 30 ng/g and lynx had 820 and 750 ng/g lw for SCCPs and MCCPs, respectively. SCCPs was included in the POPs Regulation (EC) 850/2004 by the amendment (EU) 2015/2030 in 2015. So far MCCPs are not globally regulated, however, SCCPs has recently been included in the Stockholm Convention, and a global regulation will be effectuated within November 2019.
Organophosphorous flame retardants (OPFR)
The global use of phosphorous containing flame retardants in 2001 was 186 000 tonnes (Marklund et al., 2005). Arylphosphate is used as a flame retardant, but also as a softener in PVC and ABS.
They are also used as flame retardants in hydraulic oils and lubricants. Some PFRs are known to be very toxic. PFRs can be either inorganic or organic, and the organic PFRs can be divided into non-halogen PFRs and halogenated PFRs. In the halogenated PFRs chlorine is the most common halogen (Hallanger et al., 2015). In this study both halogenated and non-halogen organic PFRs are included. The chlorinated OPFR compounds are thought to be sufficiently stable for short- and medium-range atmospheric transportation (Regnery and Püttmann, 2009), and observations of PFRs in the marine environment (Bollmann et al., 2012) and in remote areas (Aston et al., 1996; Regnery and Püttmann, 2009, 2010), such as glacier-ice in the Arctic and particulate organic matter in Antarctic (Ciccioli et al., 1994; Hermanson et al., 2005) suggests that some PFRs are subject to long-range transport (Möller et al., 2012).
